Resinous aromatic acid salts of a guanidine as mothproofers



Patented F eb. 28, 1956 time RESINOUS mom'ric ACID .SAL'TS or A.'GUANIDINE'AS MOTHPROOFERS flart'kes Migrdichian; Greenwich, Gonnassignor N. Y., a corporation of Maine.

to American Cyanamid Gompany, New York,

No Drawing. Continuation of application Serial No. 317,174, February 3,1940;Thisapplieation November 23, 1944, Serial No. 564,897

2 Claims.

heavy dose of the above composition acquires a greasy feel isobjectionable.

The principal object of the present invention, therefore, is to providea guanidine or substituted guanidine salt suitably soluble forapplication to fabric which will effectively protect such cloth againstthe ravages of the carpet beetle and/orv webbing clothes moth larvaewithout taking on this objectionable feel, even in heavy dosages.

It has been discovered that salts of guanidines or substitutedguanidines may be obtained by reactin the free guanidine or substitutedguanidine with aromatic acids. A large number of these compounds havebeen prepared and the very remarkable discovery made that all oi? thesesalts are of a resinous character. This is a desirable characteristic ina substance used for mothproofing in that it has a tendency to adhere tothe fabric when deposited thereon from its solution. In the case ofcrystalline mate rial, the deposited crystals of the salt may be brushedor rubbed therefrom with consequent loss of mothproofingcharacteristics.

While the dixylyl guanidine salt of an aromatic acid is preferred, yetother mono or poly substituted guanidine salts thereof are useful,

such as those of the alkyl, aryl, and alkyl aryl groups, as well as theunsubstituted guanidine salts. Any of the aromatic acids may be used,such as benzoic, salicylic, anthranilic, phthalic, or the like.

These compounds may be readily prepared by dissolvin the acid inalcohol, adding the equivalent quantity of the free guanidine orsubstituted guanidine, and evaporating off the excess alcohol. They mayalso be made by adding equivalent quantities of the guanidine orguanidine compound to the molten acid.

These guanidine and substituted guanidine salts are fusible, so that analternative convenient method of preparing them is to add a mixture inequivalent quantities of the acid and the free guanidine or substitutedguanidine to the fused guanidine salt, heating until all soliddisappears, whereupon combination to the salt takes place almostinstantaneously.

Still another method which avoids the necessity of evaporating ofi largequantities of alcohol, is to dissolve a small portion of the mixture ofthe acid and free or substituted guanidine in warm alcohol and addingmore of the mixture while the liquid is kept hot. Proceeding'in thismanner and starting with a comparatively small quantity of alcohol, anyamount of the corresponding salt containing the guanidine group may beprepared. The small amount of alcohol in the final product is notobjectionable and may be eliminated if so desired by grinding thechilled product and drying in the usual manner.

These compounds are not soluble to any great extent in petroleumfractions but are to a limited extent in chlorinated hydrocarbons and inaromatic hydrocarbons. They are quite soluble in alcohol. The solubilityof these compounds in petroleum hydrocarbons may be increased by theaddition of alcohol. To the alcoholic solutions thereof, largeproportions of tetrachloride may be added without causing precipitation.The addition of this last substance to their alcoholic solutions, in aquantity at least equal to the amount of alcohol used, to a large degreeeliminates the fire hazard attendant upon the use of alcohol alone.

From 1 to 5% of the guanidine compound may be readily dissolved in anethyl alcohol-carbon tetrachloride mixture containing 10% of thealcohol. Such solutions may be sprayed on the cloth at the rate of onegallon to from ten to thirty pounds of cloth, or the cloth may be dippedin the solution, wrung out and then dried.

A medium weight white Wool flannel, a brown Wool cloth and a woolensuiting were used in a series of tests with salts of the above acidscontaining a guanidine group. The compounds were applied in solution ina mixed alcohol-carbon tetrachloride solvent at various rates and theresistance of the treated pieces to the attack of black carpet beetleand webbing clothes moth larvae tested. All solutions contained aquantity of the guanidine salt equivalentto approximately 3%. Allsamples of cloth whichhad had an application equivalent to as much asone gallon per ten pounds of cloth had complete protection. Thisresistance to destruction by the above insects was ineiiective only whenthe application dropped to one-third of a gallon per ten pounds ofcloth. The present application is a continuation of my copendingapplication Serial No. 317,174, filed February 3, 1940, now abandoned.

Many of the above substances are new chemical compounds.

While the invention has been described with particular reference tospecific embodiments, it REFERENCES CITED i t be u t od that, t, i t, tb limited The following references are of record in the thereto but isto be construed broadly and refile of this patent: striated solely bythe scope of the appended 5 UNITED STATES PATENTS c a s.

I hu Number Name Date 1. A mothproofing composition containing a 2,1 1,27 ter Hor p 1938 guanidine salt of benzoic acid dissolved in a2,145,214 Jayne Jan. 24, 1939 mixture of ethyl alcohol and carbontetrachlo- 10 2,233,680 Sibley Mar. 4, 1941 ride. 2,256,759 Ham Sept.23, 1941 2. A mothproofing composition containing a 2,347,688 Jayne May2, 1944 dixylyl guanidine salt of benzoic acid dissolved in a mixture ofethyl alcohol and carbon tetrachloride. 15

VARTKES MIGRDICELAN.

1. A MOTHPROOFING COMPOSITION CONTAINING A GUANIDINE SALT OF BENZOICACID DISSOLVED IN A MIXTURE OF ETHYL ALCOHOL AND CARBON TETRACHLORIDE.